The reactivity of 1,1-dichloro-2,2-di-tert-butyldiphosphane towards lithiated metal carbonyls: a new entry to phosphanylphosphinidene dimers

Grubba, Rafał; Zauliczny, Mateusz; Ponikiewski, Łukasz; Pikies, Jerzy

doi:10.1039/c5dt04983k

Cited by 8 publications

(5 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Relativistic effects were included using the scalar zeroth‐order regular approximation (scalar ZORA) model . The functional and basis sets were chosen according to our experience,, , on the grounds that they describe molecules of our interest well, while maintaining a moderate computational cost. Additionally, one can easily relate the results of this work with the one previously published by our group, as the same basis set and functional were applied.…”

Section: Computational Detailsmentioning

confidence: 99%

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, ³¹P NMR Spectra, and Reactivities

et al. 2018

Self Cite

View full text Add to dashboard Cite

Theoretical studies of the bonding interactions and most important properties are carried out for isolable phosphanylphosphinidene complexes of transition metals. Three main types of phosphanylphosphinidene complexes are distinguished, based on the way in which the phosphanylphosphinidene ligand bonds to the metal center: (i) side-on complexes of platinum, where the R 2 P -P α ligand mimics structural features of free singlet phosphanylphosphinidenes with short, polarized, double P-P bonds and two lone electron pairs on the terminal P atom. In this case, interactions between the platinum center and the phosphanylphosphinidene ligand are determined by π(PP)→s(Pt) donation and d(Pt)→π*(PP) back-dona- [a]

show abstract

Section: Computational Detailsmentioning

confidence: 99%

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, ³¹P NMR Spectra, and Reactivities

et al. 2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…A similar bonding mode is observed in complex 3c , where dicationic t Bu 2 P + P–PP + t Bu 2 ligand coordinates to two platinum metal centers. Notably, based on our previous calculations, the phosphorus ligands in dimeric complexes [Cp*M(CO) 3 (η 2 - t Bu 2 PP)] 2 (M = Mo, W) possess analogous Lewis structures …”

Section: Resultsmentioning

confidence: 88%

“…The platinumphosphorus bonds in 3c and in parent complex 3 have very similar lengths. Dimeric molybdenum and tungsten complexes with analogous t Bu 2 PPPP t Bu 2 ligands were previously synthesized by our group from the reaction of Li[Cp*(CO) 3 ] with t Bu 2 P–PCl 2 . The tetraphosphorus ligands in these complexes displayed geometries very similar to the corresponding ligand in 3c .…”

Section: Resultsmentioning

confidence: 99%

“…Notably, based on our previous calculations, the phosphorus ligands in dimeric complexes [Cp*M(CO) 3 (η 2 -tBu 2 PP)] 2 (M = Mo, W) possess analogous Lewis structures. 46 Consequently, we performed analogous calculations for free phosphenium cations tBu 2 P + P−Me (I),tBu 2 P + P−I (II) and (tBu 2 P + P) 2 (III). On the basis of our calculations, these species have a singlet ground state.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

The Reactivity of Phosphanylphosphinidene Complexes of Transition Metals Toward Terminal Dihaloalkanes

et al. 2020

Self Cite

View full text Add to dashboard Cite

The reactivities of phosphanylphosphinidene complexes [(DippN) 2 W(Cl)(η 2 -P–P t Bu 2 )] − ( 1 ), [( p Tol 3 P) 2 Pt(η 2 -P=P t Bu 2 )] ( 2 ), and [(dppe)Pt(η 2 -P=P t Bu 2 )] ( 3 ) toward dihaloalkanes and methyl iodide were investigated. The reactions of the anionic tungsten complex ( 1 ) with stochiometric Br(CH 2 ) n Br ( n = 3, 4, 6) led to the formation of neutral complexes with a t Bu 2 PP(CH 2 ) 3 Br ligand or neutral dinuclear complexes with unusual tetradentate t Bu 2 PP(CH 2 ) n PP t Bu 2 ligands ( n = 4, 6). The methylation of platinum complexes 2 and 3 with MeI yielded neutral or cationic complexes bearing side-on coordinated t Bu 2 P–P-Me moieties. The reaction of 2 with I(CH 2 ) 2 I gave a platinum complex with a t Bu 2 P—P—I ligand. When the same dihaloalkane was reacted with 3 , the P—P bond in the phosphanylphosphinidene ligand was cleaved to yield t Bu 2 PI, phosphorus polymers, [(dppe)PtI 2 ] and C 2 H 4 . Furthermore, the reaction of 3 with Br(CH 2 ) 2 Br yielded dinuclear complex bearing a tetraphosphorus t Bu 2 PPPP t Bu 2 ligand in the coordination sphere of the platinum. The molecular structures of the isolated products were established in the solid state and in solution by single-crystal X-ray diffraction and NMR spectroscopy. DFT studies indicated that the polyphosphorus ligands in the obtained complexes possess structures similar to free phosphenium cations t Bu 2 P + =P−R (R = Me, I) or ( t Bu 2 P + =P) 2 .

show abstract

“…The P−W distances are comparable to those observed for dinuclear tungsten complexes containing the catena-polyphosphorus ligands. 42,51 The P4−S2 bond length (2.039(2) Å) suggests π-interactions contribute significantly (sum of single-bond covalent radii for P and S = 2.14 Å; sum of double bond covalent radii for P and S = 1.96 Å). 45,49 Scheme 2.…”

Section: Resultsmentioning

confidence: 99%

Syntheses and Structures of Transition Metal Complexes with Phosphanylphosphinidene Chalcogenide Ligands

et al. 2019

Self Cite

View full text Add to dashboard Cite

The reactivity of the phosphanylphosphinidene complex [(DippN)2W(Cl)(η2-P-PtBu2)]− (1) toward chalcogens (Ch = Se, S) was studied. Reactions of stoichiometric amounts of 1 with chalcogens in DME yielded monomeric tungsten complexes with phosphanylphosphinidene chalcogenide ligands of the formula tBu2P–P–Ch (Ch = Se (in 2) and S (in 5)), which can be regarded as products of the addition of a chalcogen atom to a PW bond in starting complex 1. The dissolution of selenophosphinidene complex 2 in nondonor solvents led to the formation of a dinuclear complex of tungsten (3) bearing a tBu2P(Se)–P ligand together with [tBuSe2Li(dme)2]2 and polyphosphorus species. Under the same reaction conditions, thiophosphinidene complex 5 dimerized via the formation of transient complex 7, possessing a thiotetraphosphane-diido moiety tBu2P(S)–P–P–PtBu2. The elimination of the tBu2PS group from 7 yielded stable dinuclear tungsten complex 8 with an unusual phosphinidene tBu2P–P–P ligand. The reaction of 1 with excess chalcogen led to the cleavage of the P–P bond in the tBu2P–P ligand and the formation of [(DippN)2W(PCh4)]2 2– and [tBuCh2Li(dme)2]2. The isolated compounds were characterized by NMR spectroscopy and X-ray crystallography. Furthermore, the calculated geometries of the free selenophosphinidenes, tBu2P–P–Se and tBu2P(Se)−P, were compared with their geometries when serving as ligands in complexes 2 and 3.

show abstract

The reactivity of 1,1-dichloro-2,2-di-tert-butyldiphosphane towards lithiated metal carbonyls: a new entry to phosphanylphosphinidene dimers

Abstract: Reactions of [Cp(OC)3M]Li (Cp = C5Me5, M = Mo, W) towards t-Bu2P–PCl2 lead to the formation of phosphanylphosphinidene dimers [Cp*(OC)3M(η2-t-Bu2P–P)]2 in fairly good yields.

Cited by 8 publications

References 33 publications

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, ³¹P NMR Spectra, and Reactivities

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, ³¹P NMR Spectra, and Reactivities

The Reactivity of Phosphanylphosphinidene Complexes of Transition Metals Toward Terminal Dihaloalkanes

Syntheses and Structures of Transition Metal Complexes with Phosphanylphosphinidene Chalcogenide Ligands

Contact Info

Product

Resources

About

The reactivity of 1,1-dichloro-2,2-di-tert-butyldiphosphane towards lithiated metal carbonyls: a new entry to phosphanylphosphinidene dimers

Abstract: Reactions of [Cp*(OC)3M]Li (Cp* = C5Me5, M = Mo, W) towards t-Bu2P–PCl2 lead to the formation of phosphanylphosphinidene dimers [Cp*(OC)3M(η2-t-Bu2P–P)]2 in fairly good yields.

Cited by 8 publications

References 33 publications

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, 31P NMR Spectra, and Reactivities

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, 31P NMR Spectra, and Reactivities

The Reactivity of Phosphanylphosphinidene Complexes of Transition Metals Toward Terminal Dihaloalkanes

Syntheses and Structures of Transition Metal Complexes with Phosphanylphosphinidene Chalcogenide Ligands

Contact Info

Product

Resources

About

Abstract: Reactions of [Cp(OC)3M]Li (Cp = C5Me5, M = Mo, W) towards t-Bu2P–PCl2 lead to the formation of phosphanylphosphinidene dimers [Cp*(OC)3M(η2-t-Bu2P–P)]2 in fairly good yields.

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, ³¹P NMR Spectra, and Reactivities

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, ³¹P NMR Spectra, and Reactivities